CN108339547B - Method for catalytic conversion of tar - Google Patents
Method for catalytic conversion of tar Download PDFInfo
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- CN108339547B CN108339547B CN201710049598.7A CN201710049598A CN108339547B CN 108339547 B CN108339547 B CN 108339547B CN 201710049598 A CN201710049598 A CN 201710049598A CN 108339547 B CN108339547 B CN 108339547B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
Abstract
The invention relates to a method for catalytically converting tar, which comprises the steps of mixing tar, methanol or methanol aqueous solution and a supported nickel-based catalyst, heating the obtained mixture to ensure that the tar is subjected to hydrodeoxygenation reaction, cooling after the reaction is finished, and collecting liquid to obtain a refined oil product after catalytic conversion. According to the invention, methanol or methanol aqueous solution and the supported nickel-based catalyst are selected to carry out catalytic hydrogenation treatment on tar, so that a series of cost and safety problems related to transportation, storage and operation caused by the large amount of external hydrogen are avoided, and meanwhile, compared with a noble metal supported catalyst and a Ni-Al alloy catalyst, the Ni-based supported catalyst with low price is adopted, so that the cost is favorably reduced. The method has the advantages of high catalytic efficiency, low cost, simple method, no toxicity of used reagents, mild operating conditions, easy collection of products and the like, is favorable for reducing the cost and improving the production profit, and has good industrialization prospect.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a method for catalytically converting tar.
Background
The tar obtained in the dry distillation process of the coal or the biomass is a complex mixture system and is a cheap fuel source. However, because the complicated composition of the components in the pyrolysis tar, especially the high content of phenolic substances, causes the tar to have higher oxygen content, acidity, corrosiveness and polarity, and lower calorific value, and limits the application of the tar as liquid fuel or blending with gasoline and diesel oil, it is necessary to perform a refining treatment on the tar to reduce the content of phenolic substances in the tar and increase the content of aromatic hydrocarbons, thereby reducing the acidity, corrosiveness and polarity of the tar and increasing the calorific value of the tar. The polarity of tar is an important factor influencing the blending effect of the tar and gasoline and diesel, namely the higher the polarity of tar is, the better the water solubility is, and the poorer the oil solubility is, the more adverse the tar is used as a blending component of gasoline and diesel.
At present, the main tar refining schemes are as follows: distillation and separation technology of components for separating components, catalytic hydrogenation of tar, catalytic cracking, deoxidation and refining, etc. Because the components of the tar are very complex, the measured components are more than 200, and the content of any single component in the tar is very low, the scheme for obtaining high-purity single chemicals through multistage series rectification operation has extremely high energy consumption, and the distillation process is often accompanied with the thermal polycondensation reaction of unstable components in the tar, particularly the content of unstable components in low-temperature tar is higher, so that the yield of target products is extremely low, and therefore, the component rectification separation process is mainly suitable for high-temperature coal tar and is less used for refining medium-temperature and low-temperature coal tar. The catalytic pyrolysis deoxidation technology attempts to break C-O bonds in oxygen-containing components of tar and make oxygen atoms in the form of CO and CO through high-temperature catalysis2And H2And removing the O form, thereby achieving the purposes of reducing the oxygen atom content in the product oil, further improving the calorific value of the product oil and reducing the acidity and polarity of the product oil. However, the technology still stays in the laboratory research stage at present and is far from practical application because the carbon deposition phenomenon is serious in the reaction process, so that the activity of the catalyst is rapidly reduced, and the regenerability and the service life of the catalyst are also remarkably deteriorated along with the prolonging of the reaction time.
The biological oil and the medium and low temperature coal tar mainly take hydrogenation oil preparation as a target, and because the introduction of hydrogen can remove oxygen atoms in the tar in the form of water and is beneficial to avoiding the generation of carbon deposition on the surface of a catalyst, the method is a technical scheme with the best deoxidation effect, the service life of the catalyst and the regenerability of the catalyst, and has already realized industrial application. However, the use of gaseous hydrogen in this technique brings about many potential safety hazards related to the storage, transportation and operation of hydrogen, and particularly, the reaction between hydrogen and tar has an interphase interface, which results in a limited transfer rate and is not favorable for increasing the reaction rate.
In view of the defects of high safety risk of hydrogen storage and transportation and operation and low gas-liquid interphase reaction rate of the conventional tar hydroconversion reaction system, an in-situ reaction hydrogenation scheme of replacing gaseous hydrogen with a liquid hydrogen supply reagent is provided. The tar in-situ hydrogenation technology is characterized in that a reaction system provides a hydrogen source required by reaction under the condition of no external hydrogen supply, common hydrogen supply reagents mainly comprise oxygen-containing compounds such as micromolecule alcohol, aldehyde, ketone, acid and the like, hydrogen and active hydrogen atoms are generated through the water-phase reforming reaction of the micromolecule oxygen-containing compounds, and the active hydrogen atoms can directly react with the oxygen-containing components, so that the catalytic dissociation, activation and conversion processes of gaseous hydrogen are avoided.
Research has shown that noble metal supported catalysts such as Pd, Pt, Ru and the like and Raney Ni (Ni-Al alloy) catalysts have good in-situ hydrogenation catalytic activity when formic acid is used as a hydrogen supply reagent. However, the metal-supported catalyst is expensive and difficult to industrially popularize on a large scale. Compared with a noble metal supported catalyst and a Ni-Al alloy catalyst, the Ni-based supported catalyst is low in price and simple in preparation method, so that the Ni-based supported catalyst has higher application and development values.
Disclosure of Invention
The invention provides a method for catalytically converting tar, which aims to overcome the defects in the prior art, and adopts methanol or a methanol aqueous solution as a reaction solvent and a hydrogen supply reagent and selects a Ni-based supported catalyst to catalytically convert the tar, so that the cost and safety problems related to a series of transportation, storage and operation caused by the large use of external hydrogen are avoided, and meanwhile, compared with a noble metal supported catalyst and a Ni-Al alloy catalyst, the cost is reduced by adopting the low-price Ni-based supported catalyst. The method has high catalytic efficiency, the highest heat value increasing rate of the refined tar can reach more than 90 percent compared with the initial tar, the highest water removal rate can reach more than 85 percent, and the method is simple, has low cost and is suitable for industrial popularization.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for catalytically converting tar, the method comprising: mixing tar, methanol or methanol aqueous solution and a supported nickel-based catalyst, heating the obtained mixture to perform hydrodeoxygenation reaction on the tar, cooling after the reaction is finished, and collecting liquid to obtain a refined oil product after catalytic conversion.
In view of the fact that the tar in-situ hydrodeoxygenation conversion scheme has more remarkable storage, transportation and operation safety advantages than the tar hydrogenation scheme taking hydrogen as hydrogen source, the invention researches the tar in-situ hydrodeoxygenation conversion of various supported metal catalysts. Researches find that the matching and synergistic effect between the catalyst and the hydrogen supply reagent have obvious influence on the in-situ hydrodeoxygenation reaction effect of the tar, but the influence effect and the influence degree are different. When formic acid is used as a hydrogen supply reagent, the catalytic effect of noble metal loaded catalysts such as Pd, Pt and Ru is high, and the catalytic effect of Ni-based loaded catalysts is poor; on the contrary, when methanol is used as a hydrogen donor, the catalytic effect of the noble metal supported catalyst such as Pd, Pt, Ru and the like is reduced, and the catalytic effect of the Ni-based supported catalyst is remarkably improved. The reason for this is that the hydrogen-donating conversion products of different hydrogen-donating agents contain different contents of CO and CO in addition to hydrogen2And like other products, CO or CO2Different degrees of competitive adsorption with hydrogen occur on the surfaces of different catalysts, and the hydrogen-donating conversion products of different hydrogen-donating agents under different conditions have different compositions, so that the influence effects and the influence degrees of different hydrogen-donating agents on different metal-loaded catalysts are different.
According to the invention, the tar is any one or a combination of at least two of bio-oil, coal tar or phenol-rich oil separated from bio-oil or coal tar, for example, any one of bio-oil, coal tar or phenol-rich oil separated from bio-oil or coal tar, and typical but non-limiting combinations are as follows: biological oil and coal tar, biological oil and phenol-rich oil separated from the biological oil or the coal tar, coal tar and phenol-rich oil separated from the biological oil or the coal tar, biological oil, coal tar and phenol-rich oil separated from the biological oil or the coal tar.
The tar, whether coal tar or bio-oil or phenol-rich oil obtained by separating the coal tar and the bio-oil, has very complex component composition and generally has the defects of high oxygen content, strong acidity, high polarity, low heat value and the like, the higher the polarity of the tar is, the more unfavorable the tar is used as a blending component of gasoline and diesel, and the lower the heat value is, the lower the application efficiency is.
The refined oil product refers to a product obtained by performing catalytic conversion on a tar raw material by using the method provided by the invention, and the components of the obtained refined oil product are different due to different raw materials.
According to the invention, the mass ratio of tar, methanol or aqueous methanol solution and supported nickel-based catalyst is 1 (2-10): (0.1-1), and may be, for example, 1:2:0.1, 1:3:0.2, 1:4:0.3, 1:5:0.4, 1:6:0.5, 1:7:0.6, 1:8:0.7, 1:9:0.8 or 1:10:1, and the specific values between the above values, limited to space and for the sake of brevity, are not exhaustive and are not exhaustive.
In the invention, the mass ratio of tar, methanol or methanol aqueous solution and the supported nickel-based catalyst is preferably 1 (2-5) to (0.2-5).
According to the invention, the mass ratio of methanol to water in the aqueous methanol solution is (0.8-20):1, and may be, for example, 0.8:1, 1:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 18:1 or 20:1, and the specific values between the above values are limited to space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the ranges.
In the present invention, the mass ratio of methanol to water in the aqueous methanol solution is preferably (3-15): 1.
When the hydrogen supply reagent is pure methanol, the hydrogen source in the system mainly comes from hydrogen or active hydrogen atoms generated by the methanol decomposition reaction; when the hydrogen-supplying reagent is methanol water solution, the hydrogen source in the system mainly comes from hydrogen or active hydrogen atoms generated by water-phase reforming reaction between methanol and water. The obtained hydrogen or active hydrogen atoms provide reducing agents for the hydrodeoxygenation reaction of the tar.
According to the present invention, the temperature of the hydrodeoxygenation reaction is 220-320 ℃, and may be, for example, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃ or 320 ℃, and specific values therebetween are not limited to the space and the specific values included in the range are not exhaustive for the sake of brevity.
The temperature of the hydrodeoxygenation reaction in the present invention is preferably 250-280 ℃.
According to the invention, the hydrodeoxygenation reaction time is between 1 and 6h, and may be, for example, 1h, 2h, 3h, 4h, 5h or 6h, and the values between the above values are specific, for reasons of space and simplicity, and the invention is not intended to be exhaustive.
The time of the hydrodeoxygenation reaction in the invention is preferably 2 to 4 hours.
The catalytic conversion of tar according to the present invention is carried out in a reaction vessel commonly used in the art, and for example, a pressurized reaction vessel, a pressurized slurry bed, a pressurized fixed bed or a pressurized tubular reactor, etc. can be selected, but not limited thereto. When operating under laboratory conditions, it is preferred to use a pressurized reaction vessel.
According to the present invention, the loading of nickel in the supported nickel-based catalyst is 1-50 wt%, for example, 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt% or 50 wt%, and specific values between the above values, which are not limited by space and for the sake of brevity, are not exhaustive and are not included in the recited ranges.
The loading amount of nickel in the supported nickel-based catalyst in the invention is preferably 5-20 wt%;
according to the invention, the supported nickel-based catalyst is prepared by the following method:
(1) loading a nickel salt solution on a carrier by adopting an isometric impregnation method, and drying after aging;
(2) calcining the dried sample;
(3) and carrying out reduction treatment on the calcined sample to obtain the supported nickel-based catalyst.
According to the invention, the nickel salt in the nickel salt solution in step (1) is any one or a combination of at least two of nickel chloride, nickel sulfate, nickel nitrate, nickel acetate or nickel oxalate, for example, any one of nickel chloride, nickel sulfate, nickel nitrate, nickel acetate or nickel oxalate, and typical but non-limiting combinations are as follows: nickel chloride and sulfate, nickel nitrate and acetate, nickel chloride and nitrate, nickel acetate and oxalate, nickel chloride, sulfate and nitrate, nickel nitrate, acetate and oxalate, etc., are not exhaustive for the invention, but for reasons of space and brevity.
According to the invention, the concentration of the nickel salt solution in step (1) is 10-50 wt%, for example 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt% or 50 wt%, and the specific values between the above values, which are limited by space and for the sake of brevity, are not exhaustive and are not included in the range.
The concentration of the nickel salt solution in the step (1) in the present invention is preferably 10 to 40 wt%.
According to the invention, the carrier in the step (1) is activated carbon or Al2O3、ZrO2、SiO2Any one or combination of at least two of MCM-41, MCM-48, SBA-15, FSM-16, MSU-1 or HMS, such as activated carbon, Al2O3、ZrO2、SiO2Any one of MCM-41, MCM-48, SBA-15, FSM-16, MSU-1 or HMS, with a typical but non-limiting combination being activated carbon and Al2O3Activated carbon and ZrO2，Al2O3And ZrO2，SiO2And MCM-41, MCM-48 and SBA-15, FSM-16 and MSU-1, activated carbon, Al2O3And ZrO2，SiO2MCM-41 and HMS, etc., are not exhaustive for the invention, both for space and for brevity.
In the present invention, the carrier in the step (1) is preferably Al2O3And/or ZrO2。
In the present invention, when the average pore diameter of the carrier is 0.7 to 20nm, it is advantageous to improve the activity of the catalyst.
According to the invention, the aging time of step (1) is 10-20h, for example 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h or 20h, and the specific values between the above values are not exhaustive for the sake of brevity and simplicity.
According to the invention, the drying operation in step (1) is as follows: drying the aged sample at 25-35 deg.C for 1-6h, and drying at 40-60 deg.C for 3-12h, preferably at 30 deg.C for 3h, and drying at 50 deg.C for 8 h.
The selection of the drying temperature, the drying time and the drying step influences the effect of loading the metal salt, and the two-step drying method is favorable for avoiding the agglomeration of the loaded metal salt, further is favorable for reducing the particle size of the reduced metal and improving the specific surface area of the loaded metal particles.
According to the present invention, the temperature of the calcination in step (2) is 400-700 ℃, for example, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃ or 700 ℃, and the specific values between the above values are limited by the space and for the sake of brevity, and the present invention is not exhaustive list of the specific values included in the range.
According to the invention, the calcination time in step (2) is 3-8h, for example 3h, 4h, 5h, 6h, 7h or 8h, and the specific values between the above values are limited by space and for the sake of brevity, and the invention is not intended to be exhaustive.
According to the invention, the operation of the reduction treatment in step (3) is: the calcined sample is treated at 400-600 ℃ in H2Or H2Treating for 2-8h in a mixed atmosphere of inert gas.
When in H2In the reduction treatment, the catalyst may be sintered due to the exothermic effect, resulting in deterioration of the catalyst performance, and therefore the reduction treatment is preferably carried out in the presence of H2And mixed with inert gas.
The temperature of the calcination in the reduction treatment is 400-.
The calcination time in the reduction treatment is 2-8h, for example, 2h, 3h, 4h, 5h, 6h, 7h, 8h, and the specific values between the above values are limited by space and for the sake of brevity, and the invention is not exhaustive.
According to the invention, the inert gas is N2Any one or a combination of at least two of Ar and He, for example, N2Any one of Ar or He, with a typical but non-limiting combination being N2And Ar, N2And He, Ar and He, N2Ar and He.
According to the invention, H in said mixed atmosphere2Is 10-90%, for example 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90%, and the particular points between the above values, are not exhaustive and for simplicity, the invention is not intended to be limited to the specific points included in the recited ranges.
According to the invention, H in said mixed atmosphere2The volume percentage of (B) is preferably 40-60%.
The supported nickel-based catalyst prepared by the method and the conditions and methanol or methanol aqueous solution are selected to carry out catalytic conversion on tar, so that the tar quality can be improved, a product with higher heat value and lower water content can be obtained, and when the preparation conditions exceed or fall below the range, the catalytic efficiency is obviously reduced.
As a preferred technical scheme, the method for catalytically converting tar comprises the following steps:
(a) loading a nickel salt solution with the concentration of 10-40 wt% on Al by adopting an equal-volume impregnation method2O3And/or ZrO2After aging for 10-20H, drying at 30 ℃ for 3H, then drying at 50 ℃ for 8H, then calcining at 400-700 ℃ for 3-8H, and after calcining at 400-600 ℃ and H2Or H2Reducing the catalyst in the mixed atmosphere of inert gas for 2 to 8 hours to obtain a supported nickel-based catalyst; wherein, H in the mixed atmosphere2The volume percentage of (A) is 40-60%; the loading amount of nickel in the supported nickel-based catalyst is 5-20 wt%;
(b) mixing tar, methanol or methanol aqueous solution and the supported nickel-based catalyst obtained in the step (a) according to the mass ratio of 1 (2-5) to (0.2-5), heating the obtained mixture at the temperature of 250 ℃ for 2-4h to ensure that the tar is subjected to hydrodeoxygenation reaction, cooling after the reaction is finished, and collecting liquid to obtain refined tar after catalytic conversion; wherein the mass ratio of methanol to water in the methanol aqueous solution is (3-15): 1.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the method for catalytically converting tar has high catalytic efficiency, the heat value of the tar before and after conversion reaches 30-40MJ/kg from 17-35MJ/kg, the heat value increasing rate can reach more than 90 percent at most, the water content of the tar is reduced to 3-5 percent from 8-32 percent, and the water removal rate can reach more than 85 percent at most.
(2) Methanol or methanol aqueous solution is selected as a reaction solvent and a hydrogen supply reagent, so that a series of cost and safety problems related to transportation, storage and operation caused by the large-scale use of external hydrogen are avoided.
(3) The Ni-loaded catalyst has low cost, simple preparation and tar conversion methods, non-toxic reagent, mild operation conditions, easy collection of products, contribution to reducing cost and improving production profit and good industrialization prospect.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In order to evaluate the polarity change after the hydrodeoxygenation conversion of the tar, the water content in the tar is measured by adopting a Karl Fischer method, and the higher the water content is, the higher the polarity is, otherwise, the lower the polarity is.
In order to quantitatively analyze the gas phase product obtained by the tar conversion, the following examples were carried out by filling an inert gas into a high-pressure reaction vessel to an initial pressure of 1MPa and measuring the cumulative amount of the filled inert gas by a flow meter before heating the mixture, but the inert gas was not required to be filled at the time of actual production.
Example 1
Preparing a catalyst: immersing 11g of Al with the average pore diameter of 7.5nm in 27 wt% nickel nitrate solution by an equal-volume immersion method2O3On the particles, Al impregnated with nickel nitrate2O3Standing the granules at room temperature for 12h, and then drying the granules in a 30 ℃ oven for 3h and then drying the granules in a 50 ℃ oven for 8 h; then calcining for 5 hours at 500 ℃; passing the whole calcined supported catalyst precursor through a tube furnace at 50% H with the flow rate of 300mL/min2And (3) heating to 550 ℃ in a mixed gas environment of 50% Ar gas, and keeping for 2 hours to obtain the metal supported catalyst.
Catalytic conversion of tar: 20g of straw fast pyrolysis bio-oil (heat value 17MJ/kg, water content 32%, phenol content 33%, carboxylic acid content 7%, five-membered ring oxygen-containing compound content 16%, other component content 12%), 4g of water, 36g of methanol and 4g of catalyst are loaded into a high-pressure reaction kettle with the volume of 100mL, and N is charged into the reaction kettle2Thirdly, blowing the air in the reaction kettle, and continuously filling N2So that the initial pressure in the kettle reaches 1 MPa. And (3) heating the reaction kettle to 260 ℃, standing for 4 hours at the temperature, transferring the reaction kettle to cold water after the reaction is finished, cooling to room temperature, and collecting gas and liquid products in the kettle for quantitative analysis after the temperature of the reaction kettle is stable.
The test analysis results show that: in the catalyst and an oil phase product obtained by converting tar under reaction conditions, the content of methyl carboxylate is 8%, the content of furan derivatives is 21%, the content of cyclohexane derivatives is 34%, the content of aromatic hydrocarbon is 11%, the content of other components is 21%, the water content is 5%, and the heat value is 31 MJ/kg.
Example 2
Preparing a catalyst: immersing nickel chloride solution with the concentration of 24 wt% in 13g of Al with the average pore diameter of 7.5nm by adopting an equal-volume immersion method2O3On the particles, Al impregnated with nickel nitrate2O3Standing the granules at room temperature for 12h, and then drying the granules in a 30 ℃ oven for 3h and then drying the granules in a 50 ℃ oven for 8 h; then calcining for 5 hours at 500 ℃; all calcined supported catalyst precursors are subjected to reactionThe body was passed through a tube furnace at 50% H at a flow rate of 300mL/min2And (3) heating to 550 ℃ in a mixed gas environment of 50% Ar gas, and keeping for 2 hours to obtain the metal supported catalyst.
Catalytic conversion of tar: 20g of willow coal low-temperature pyrolysis tar (27 MJ/kg of heat value, 10 percent of water content, 37 percent of phenolic matter content, 17 percent of aromatic hydrocarbon and chain hydrocarbon content, 16 percent of condensed ring hydrocarbon content and 20 percent of other components), 44g of methanol and 6g of catalyst are filled into a high-pressure reaction kettle with the volume of 150mL, N is charged into the reaction kettle2Thirdly, blowing the air in the reaction kettle, and continuously filling N2The initial pressure in the kettle reaches 1MPa, and the cumulative amount of the filled nitrogen is measured by a flowmeter. And (3) heating the reaction kettle to 280 ℃, standing for 4 hours at the temperature, transferring the reaction kettle to cold water after the reaction is finished, cooling to room temperature, and collecting gas and liquid products in the kettle for quantitative analysis after the temperature of the reaction kettle is stable.
The test analysis results show that: in the catalyst and an oil phase product obtained by converting tar under reaction conditions, the content of cyclohexane derivatives is 33 percent, the content of aromatic hydrocarbon and chain hydrocarbon is 22 percent, the content of condensed ring hydrocarbon is 19 percent, the content of other components is 23 percent, the water content is 3 percent, and the heat value is 35 MJ/kg.
Example 3
Preparing a catalyst: dipping a nickel acetate solution with the concentration of 14 wt% on 11g of activated carbon particles with the average pore diameter of 0.7nm by an equal-volume dipping method, standing the activated carbon particles dipped with nickel nitrate at room temperature for 12h, then drying the activated carbon particles in an oven at the temperature of 30 ℃ for 3h, and then drying the activated carbon particles in an oven at the temperature of 50 ℃ for 8 h; then calcining for 5 hours at 500 ℃; passing all calcined supported catalyst precursor through a tube furnace at pure H with the flow rate of 300mL/min2And (3) raising the temperature to 550 ℃ under the environment, and keeping the temperature for 2 hours to obtain the metal supported catalyst.
Catalytic conversion of tar: the method comprises the steps of filling 6g of water, 36g of methanol and 2g of catalyst into a high-pressure reaction kettle with the volume of 150mL, filling nitrogen into the reaction kettle for three times to purge air in the reaction kettle, continuously filling nitrogen to enable the initial pressure in the kettle to reach 1MPa, and metering the accumulation amount of the filled nitrogen through a flowmeter, wherein the heat value of the Hela coal medium-temperature pyrolysis tar is 34MJ/kg, the water content is 8%, the phenol content is 22%, the aromatic hydrocarbon and chain hydrocarbon content is 26%, the fused ring hydrocarbon content is 24%, and the other components are 20%. And (3) heating the reaction kettle to 260 ℃, standing for 4 hours at the temperature, transferring the reaction kettle to cold water after the reaction is finished, cooling to room temperature, and collecting gas and liquid products in the kettle for quantitative analysis after the temperature of the reaction kettle is stable.
The test analysis results show that: in the catalyst and an oil phase product obtained by converting tar under reaction conditions, the content of cyclohexane derivatives is 18 percent, the content of aromatic hydrocarbon and chain hydrocarbon is 29 percent, the content of condensed ring hydrocarbon is 26 percent, the content of other components is 24 percent, the water content is 3 percent, and the heat value is 40 MJ/kg.
Example 4
Preparing a catalyst: immersing a nickel nitrate solution with the concentration of 43 wt% in 12g of ZrO with the average pore diameter of 20nm by an equal-volume immersion method2On the particles, ZrO impregnated with nickel nitrate2Standing the granules at room temperature for 12h, and then drying the granules in a 30 ℃ oven for 3h and then drying the granules in a 50 ℃ oven for 8 h; then calcining for 5 hours at 500 ℃; passing the whole calcined supported catalyst precursor through a tube furnace at 50% H with the flow rate of 300mL/min2And (3) heating to 550 ℃ in a mixed gas environment of 50% Ar gas, and keeping for 2 hours to obtain the metal supported catalyst.
Catalytic conversion of tar: 20g of fermentation residue fast pyrolysis bio-oil (20 MJ/kg of heat value, 20% of water content, 43% of phenolic compounds, 6% of carboxylic acid, 12% of five-membered ring oxygen-containing compounds and 19% of other components), 5g of water, 36g of methanol and 20g of catalyst are loaded into a high-pressure reaction kettle with the volume of 150mL, nitrogen is charged into the reaction kettle for three times to purge the air in the reaction kettle, the nitrogen is continuously charged to enable the initial pressure in the kettle to reach 1MPa, and the cumulant of the charged nitrogen is measured through a flowmeter. And (3) heating the reaction kettle to 240 ℃, standing for 4 hours at the temperature, transferring the reaction kettle to cold water after the reaction is finished, cooling to room temperature, and collecting gas and liquid products in the kettle for quantitative analysis after the temperature of the reaction kettle is stable.
The test analysis results show that: in the catalyst and an oil phase product obtained by converting tar under reaction conditions, the content of methyl carboxylate is 7%, the content of furan derivatives is 13%, the content of cyclohexane derivatives is 39%, the content of aromatic hydrocarbon is 11%, the content of other components is 26%, the water content is 4%, and the heat value is 34 MJ/kg.
Example 5
Preparing a catalyst: immersing nickel acetate solution with concentration of 47 wt% in 12g of SiO with average pore diameter of 16nm by equal volume immersion method2On the particles, SiO impregnated with nickel acetate2Standing the granules at room temperature for 12h, and then drying the granules in an oven at 25 ℃ for 1h and then drying the granules in an oven at 60 ℃ for 12 h; then calcining for 6h at 400 ℃; passing the whole calcined supported catalyst precursor through a tube furnace at 20% H with the flow rate of 300mL/min240% Ar and 40% N2Heating to 400 ℃ and keeping for 8 hours under the mixed gas environment to obtain the metal supported catalyst.
Catalytic conversion of tar: 20g of pine wood meal slow pyrolysis biological oil (calorific value 22MJ/kg, water content 17%, phenolic matter content 36%, carboxylic acid content 9%, five-membered ring oxygen-containing compound content 11%, other component content 27%), 21g of water, 20g of methanol and 10g of catalyst are filled into a high-pressure reaction kettle with the volume of 150mL, and N is charged into the reaction kettle2And thirdly, blowing air in the reaction kettle, and continuously filling He to ensure that the initial pressure in the kettle reaches 2 MPa. And (3) heating the reaction kettle to 220 ℃, standing for 6 hours at the temperature, transferring the reaction kettle to cold water after the reaction is finished, cooling to room temperature, and collecting gas and liquid products in the kettle for quantitative analysis after the temperature of the reaction kettle is stable.
The test analysis results show that: in the catalyst and an oil phase product obtained by converting tar under reaction conditions, the content of methyl carboxylate is 10%, the content of furan derivatives is 12%, the content of cyclohexane derivatives is 39%, the content of aromatic hydrocarbon is 11%, the content of other components is 25%, the water content is 3%, and the heat value is 35 MJ/kg.
Example 6
Preparing a catalyst: soaking a nickel oxalate solution with the concentration of 9 wt% on 11g of MCM-41 particles with the average pore diameter of 6nm by adopting an isometric soaking method, standing the MCM-41 particles soaked with the nickel oxalate at room temperature for 12h, then drying the MCM-41 particles in a 35 ℃ drying oven for 6h, and then drying the MCM-41 particles in a 40 ℃ drying oven for 3 h; then calcining for 4h at 700 ℃; all calcined supported catalyst precursors are subjected to reactionThe body was passed through a tube furnace at 90% H at a flow rate of 300mL/min2And 10% N2Heating to 600 ℃ and keeping for 2h under the mixed gas environment to obtain the metal supported catalyst.
Catalytic conversion of tar: 20g of rice hull fast pyrolysis bio-oil (the heat value is 18MJ/kg, the water content is 31%, the content of phenolic compounds is 28%, the content of carboxylic acid is 12%, the content of five-membered ring oxygen-containing compounds is 13%, the content of other components is 16%), 190g of methanol, 10g of water and 16g of catalyst are filled into a high-pressure reaction kettle with the volume of 400mL, Ar is filled into the reaction kettle for three times to purge the air in the reaction kettle, and Ar is continuously filled to ensure that the initial pressure in the kettle reaches 3 MPa. And (3) heating the reaction kettle to 320 ℃, standing for 1h at the temperature, transferring the reaction kettle to cold water after the reaction is finished, cooling to room temperature, and collecting gas and liquid products in the kettle for quantitative analysis after the temperature of the reaction kettle is stable.
The test analysis results show that: in the catalyst and an oil phase product obtained by converting tar under reaction conditions, the content of methyl carboxylate is 16%, the content of furan derivatives is 17%, the content of cyclohexane derivatives is 33%, the content of aromatic hydrocarbon is 5%, the content of other components is 25%, the water content is 4%, and the heat value is 35 MJ/kg.
Example 7
Preparing a catalyst: soaking a nickel salt solution with nickel oxalate concentration of 9 wt% and nickel sulfate concentration of 11 wt% on 11g of MCM-48 particles with the average pore diameter of 3.5nm by adopting an isometric soaking method, standing the MCM-48 particles soaked with nickel acetate at room temperature for 12h, and then drying the MCM-48 particles in an oven at 30 ℃ for 2h and then in an oven at 60 ℃ for 3 h; then calcining for 8 hours at 600 ℃; passing the whole calcined supported catalyst precursor through a tube furnace at 10% H with the flow rate of 300mL/min2、40％N2And heating to 450 ℃ in a mixed gas environment of 50% He, and keeping for 5 hours to obtain the metal supported catalyst.
Catalytic conversion of tar: 20g of Hiragel low-temperature pyrolysis tar (the heat value is 32MJ/kg, the water content is 12 percent, the content of phenolic compounds is 28 percent, the content of aromatic hydrocarbon and chain hydrocarbon is 27 percent, the content of condensed ring hydrocarbon is 16 percent, the content of other components is 17 percent), 160g of methanol and 18g of catalyst are filled into a high-pressure reaction kettle with the volume of 300mL, He is charged into the reaction kettle for three times to purge the air in the reaction kettle, and He is continuously charged to ensure that the initial pressure in the kettle reaches 1 MPa. And (3) heating the reaction kettle to 250 ℃, standing for 5 hours at the temperature, transferring the reaction kettle to cold water after the reaction is finished, cooling to room temperature, and collecting gas and liquid products in the kettle for quantitative analysis after the temperature of the reaction kettle is stable.
The test analysis results show that: in the catalyst and an oil phase product obtained by converting tar under reaction conditions, the content of cyclohexane derivatives is 24 percent, the content of aromatic hydrocarbon and chain hydrocarbon is 29 percent, the content of condensed ring hydrocarbon is 22 percent, the content of other components is 22 percent, the water content is 3 percent, and the heat value is 39 MJ/kg.
Example 8
Preparing a catalyst: dipping a 38 wt% nickel nitrate solution on 11g of SBA-15 particles with the average pore diameter of 6nm by an equal-volume dipping method, standing the SBA-15 particles dipped with the nickel nitrate at room temperature for 12h, and then drying the SBA-15 particles in a 30 ℃ drying oven for 4h and then in a 60 ℃ drying oven for 3 h; then calcining for 3h at 450 ℃; passing the whole calcined supported catalyst precursor through a tube furnace at 40% H with flow rate of 300mL/min2And 60% N2Heating to 420 ℃ and keeping for 6 hours under the mixed gas environment to obtain the metal supported catalyst.
Catalytic conversion of tar: charging 20g of Fugu coal medium-temperature pyrolysis tar (heat value 34MJ/kg, water content 11%, phenol content 22%, aromatic hydrocarbon and chain hydrocarbon content 26%, fused ring hydrocarbon content 24%, other component content 17%), 120g of methanol, 40g of water and 4g of catalyst into a high-pressure reaction kettle with the volume of 300mL, charging Ar into the reaction kettle for three times to purge the air in the reaction kettle, and continuously charging N2So that the initial pressure in the kettle reaches 1 MPa. And (3) heating the reaction kettle to 300 ℃, standing for 2 hours at the temperature, transferring the reaction kettle to cold water after the reaction is finished, cooling to room temperature, and collecting gas and liquid products in the kettle for quantitative analysis after the temperature of the reaction kettle is stable.
The test analysis results show that: in the catalyst and an oil phase product obtained by converting tar under reaction conditions, the content of cyclohexane derivatives is 19 percent, the content of aromatic hydrocarbon and chain hydrocarbon is 29 percent, the content of condensed ring hydrocarbon is 25 percent, the content of other components is 24 percent, the water content is 3 percent, and the heat value is 37 MJ/kg.
Example 9
Preparing a catalyst: dipping a 34 wt% nickel nitrate solution on 11g of MSU-1 particles with the average pore diameter of 2.7nm by an isometric dipping method, standing the PSU-1 particles dipped with the nickel nitrate at room temperature for 12h, and then drying the PSU-1 particles in an oven at 30 ℃ for 5h and then in an oven at 50 ℃ for 7 h; then calcining for 5h at 550 ℃; passing the whole calcined supported catalyst precursor through a tube furnace at 50% H with the flow rate of 300mL/min2And heating to 500 ℃ in a mixed gas environment of 50% He, and keeping for 3h to obtain the metal supported catalyst.
Catalytic conversion of tar: 20g of walnut shell slow pyrolysis biological oil (the calorific value is 22MJ/kg, the water content is 10%, the content of phenolic substances is 34%, the content of carboxylic acid is 11%, the content of five-membered ring oxygen-containing compound is 14%, the content of other components is 31%), 20g of methanol, 20g of water and 9g of catalyst are filled into a high-pressure reaction kettle with the volume of 100mL, Ar is charged and discharged twice into the reaction kettle, He is charged and discharged once to purge the air in the reaction kettle, and N is continuously charged2So that the initial pressure in the kettle reaches 1 MPa. And (3) heating the reaction kettle to 280 ℃, standing for 3 hours at the temperature, transferring the reaction kettle to cold water after the reaction is finished, cooling to room temperature, and collecting gas and liquid products in the kettle for quantitative analysis after the temperature of the reaction kettle is stable.
The test analysis results show that: in the catalyst and an oil phase product obtained by converting tar under reaction conditions, the content of methyl carboxylate is 10%, the content of furan derivatives is 13%, the content of cyclohexane derivatives is 31%, the content of aromatic hydrocarbon is 18%, the content of other components is 24%, the water content is 4%, and the heat value is 35 MJ/kg.
Comparative example 1
Preparing a catalyst: the same as in example 1.
Catalytic conversion of tar: the same as in example 1 was repeated, except that 36g of methanol was replaced with 36g of formic acid, as compared with example 1.
The test analysis results show that: test analysis results show that: 4% of methyl carboxylate, 3% of furan derivative, 3% of cyclohexane derivative, 7% of aromatic hydrocarbon, 70% of other components, 13% of water content, 25MJ/kg of heat value and serious coking.
Comparative example 2
Preparing a catalyst: the same as example 1 was repeated except that a 20 wt% copper nitrate solution was used in place of the 29 wt% nickel nitrate solution, as compared with example 1.
Catalytic conversion of tar: the same as in example 1.
Test analysis results show that: in the catalyst and an oil phase product obtained by biological oil conversion under reaction conditions, the content of methyl carboxylate is 2%, the content of furan derivatives is 4%, the content of cyclohexane derivatives is 5%, the content of aromatic hydrocarbon is 6%, the content of other components is 68%, the water content is 15%, and the heat value is 22 MJ/kg.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (13)
1. A method for catalytically converting tar, characterized in that the method comprises: mixing tar, a methanol aqueous solution and a supported nickel-based catalyst, heating the obtained mixture to perform hydrodeoxygenation reaction on the tar, cooling after the reaction is finished, and collecting liquid to obtain a refined oil product after catalytic conversion;
the temperature of the hydrodeoxygenation reaction is 220-320 ℃; the time of the hydrodeoxygenation reaction is 1-6 h;
the tar is any one or the combination of at least two of biological oil, coal tar or phenol-rich oil separated from the biological oil or the coal tar;
the mass ratio of the tar to the methanol aqueous solution to the supported nickel-based catalyst is 1 (2-4) to 0.2-5; the mass ratio of methanol to water in the methanol aqueous solution is (0.8-20) to 1;
the supported nickel-based catalyst is prepared by the following method:
(1) loading a nickel salt solution on a carrier by adopting an isometric impregnation method, and drying after aging;
(2) calcining the dried sample;
(3) reducing the calcined sample to obtain a supported nickel-based catalyst;
the loading amount of nickel in the supported nickel-based catalyst is 1-50 wt%;
the concentration of the nickel salt solution in the step (1) is 10-50 wt%;
the average pore diameter of the carrier in the step (1) is 0.7-20 nm;
the aging time of the step (1) is 10-20 h;
the drying operation in the step (1) is as follows: drying the aged sample at 25-35 deg.C for 1-6h, and drying at 40-60 deg.C for 3-12 h;
the calcining temperature in the step (2) is 400-700 ℃; the calcining time in the step (2) is 3-8 h;
the operation of the reduction treatment in the step (3) is as follows: the calcined sample is treated at 400-600 ℃ in H2Or H2Treating for 2-8h in the mixed atmosphere of inert gas; h in the mixed atmosphere2The volume percentage of (A) is 10-90%.
2. The method according to claim 1, wherein the mass ratio of methanol to water in the aqueous methanol solution is (3-15): 1.
3. The method of claim 1, wherein the temperature of the hydrodeoxygenation reaction is 250 ℃ and 280 ℃.
4. The method of claim 1, wherein the hydrodeoxygenation reaction time is 2 to 4 hours.
5. The method of claim 1, wherein the supported nickel-based catalyst has a nickel loading of from 5 to 20 wt%.
6. The method of claim 1, wherein the nickel salt in the nickel salt solution of step (1) is any one of nickel chloride, nickel sulfate, nickel nitrate, nickel acetate or nickel oxalate or a combination of at least two of them.
7. The method of claim 1, wherein the concentration of the nickel salt solution of step (1) is 10 to 40 wt%.
8. The method of claim 1, wherein the carrier in step (1) is activated carbon, Al2O3、ZrO2、SiO2Any one or combination of at least two of MCM-41, MCM-48, SBA-15, FSM-16, MSU-1 or HMS.
9. The method of claim 8, wherein the carrier of step (1) is Al2O3And/or ZrO2。
10. The method of claim 1, wherein the drying of step (1) is performed by: drying at 30 deg.C for 3 hr, and drying at 50 deg.C for 8 hr.
11. The method of claim 1, wherein the inert gas is N2Any one of, or a combination of at least two of, Ar or He.
12. The method of claim 1, wherein the mixed atmosphere is H2The volume percentage of (A) is 40-60%.
13. The method of claim 1, wherein the method comprises the steps of:
(a) loading a nickel salt solution with the concentration of 10-40 wt% on Al by adopting an equal-volume impregnation method2O3And/or ZrO2Aging for 10-20h, and then cooling at 30 deg.CDrying for 3H, drying at 50 ℃ for 8H, calcining at 400-700 ℃ for 3-8H, and calcining at 400-600 ℃ and H2Or H2Reducing the catalyst in the mixed atmosphere of inert gas for 2 to 8 hours to obtain a supported nickel-based catalyst; wherein, H in the mixed atmosphere2The volume percentage of (A) is 40-60%; the loading amount of nickel in the supported nickel-based catalyst is 5-20 wt%;
(b) mixing tar, methanol aqueous solution and the supported nickel-based catalyst obtained in the step (a) according to the mass ratio of 1 (2-4) to (0.2-5), heating the obtained mixture at the temperature of 250 ℃ to 280 ℃ for 2-4h to enable the tar to have hydrodeoxygenation reaction, cooling after the reaction is finished, collecting liquid to obtain refined tar after catalytic conversion; wherein the mass ratio of methanol to water in the methanol aqueous solution is (3-15): 1.
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| CN105132003A (en) * | 2015-08-27 | 2015-12-09 | 中国科学院青岛生物能源与过程研究所 | Preparation method for biological aircraft fuel |
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| CN105727957A (en) * | 2014-12-09 | 2016-07-06 | 中国科学院大连化学物理研究所 | Loaded type iron-nickel phosphide catalyst material and application thereof |
| CN105132003A (en) * | 2015-08-27 | 2015-12-09 | 中国科学院青岛生物能源与过程研究所 | Preparation method for biological aircraft fuel |
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